CN109360895A - A kind of perovskite material, preparation method and its solar cell device - Google Patents
A kind of perovskite material, preparation method and its solar cell device Download PDFInfo
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- CN109360895A CN109360895A CN201811101422.2A CN201811101422A CN109360895A CN 109360895 A CN109360895 A CN 109360895A CN 201811101422 A CN201811101422 A CN 201811101422A CN 109360895 A CN109360895 A CN 109360895A
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Abstract
The present invention relates to new energy fields, more particularly to a kind of perovskite material, preparation method and its solar cell device.Perovskite material of the invention, the molecular formula of perovskite are ABX3, wherein the A is selected from C1‑x‑yExFy, the C is selected from MA and/or FA, and the E is selected from DMA, and the F is selected from one or more of Cs, Rb, K, and the B is selected from Pb and/or Sn, and the X is selected from one or more of I, Br and Cl.Perovskite material of the invention has the stability under good atmospheric conditions, and preparation process is simple, easy to operate, has the characteristics that large-scale production.Perovskite solar cell device incident photon-to-electron conversion efficiency with higher prepared by the present invention.
Description
Technical field
The present invention relates to new energy fields, more particularly to a kind of perovskite material, preparation method and its solar battery
Device.
Background technique
With the fast development of global economy and the continuous growth of population, the consumption of fossil fuel also significantly increases,
Consequent also brings serious threat to the environment that we depend on for existence in addition to the consumption for the fuel that supply falls short of demand.Cause
This, the novel green energy resource of Devoting Major Efforts To Developing become survival and development of mankind more urgent task, halogenation perovskite due to it is low at
Originally, the features such as high efficiency, it is widely studied recently as very promising solar battery obsorbing layer material.
Since organic metal perovskite is used for dye-sensitized solar cells by Miyasaka in 2009 and obtains 3.8%
Since efficiency, perovskite solar cell device is grown rapidly, but since perovskite material is to hydrone, oxygen molecule
Sensitivity is easy to degrade under environmental condition, and which prevent the commercializations of perovskite solar battery, so solving perovskite too
The long term stability problem of positive energy battery becomes its commercialized precondition.Therefore, a kind of high efficiency how is prepared, it is high
The perovskite solar battery of stability becomes a major challenge of new energy field.
Summary of the invention
In view of the foregoing deficiencies of prior art, the purpose of the present invention is to provide a kind of perovskite materials, preparation side
Method and its solar cell device, for solving in the prior art, perovskite solar battery efficiency is low, stability is poor is asked
Topic.
In order to achieve the above objects and other related objects, an aspect of of the present present invention provides a kind of perovskite material, the calcium
The molecular formula of titanium ore is ABX3, wherein A is selected from C1-x-yExFy, the C is selected from MA and/or FA, and the E is selected from DMA, the F
Selected from one or more of Cs, Rb, K, the B is selected from Pb and/or Sn, and the X is selected from one of I, Br and Cl or several
Kind.
In some implementation methods of the invention, the C1-x-yExFyMiddle x=0-0.3, y=0-0.3, preferably x=0-
0.2, y=0-0.2.
In certain embodiments of the present invention, the A is selected from MA1-x-yDMAxCsy。
In certain embodiments of the present invention, the X is selected from I3-zBrz, wherein z=0-3.
In certain embodiments of the present invention, the perovskite material is film and/or polycrystalline.
The second aspect of the present invention provides a kind of preparation method of perovskite material, comprising: provides the presoma of perovskite
Solution forms perovskite material by the precursor solution.
In certain embodiments of the present invention, the precursor solution concentration is 0.8M-1.4M, the precursor solution
Middle solvent is selected from organic solvent, is preferably selected from one or more of DMF, DMSO, GBL, NMP.
In certain embodiments of the present invention, the precursor solution is spin-coated in substrate, the substrate be selected from NiOx,
One of PTAA, PEDOT；Anti-solvent is used in the spin coating process, the anti-solvent is in toluene, chlorobenzene, ether
It is one or more of.
In certain embodiments of the present invention, further include the steps that annealing, temperature is 70 when the annealing
DEG C -100 DEG C, annealing time 5Min-10Min.
The third aspect of the present invention provides perovskite material as described above in solar battery or electroluminescent device
Purposes.
The fourth aspect of the present invention provides a kind of perovskite solar cell device, including transport layer, barrier layer, metal electricity
Pole and perovskite material as described above.
Detailed description of the invention
Fig. 1 is MA1-x-yDMAxCsyPbI3The X ray diffracting spectrum of perovskite thin film.
Fig. 2 is MA0.905DMA0.07Cs0.025PbI3-zBrzThe X ray diffracting spectrum of perovskite thin film.
Fig. 3 is MA1-x-yDMAxCsyPbX3Scanning electron microscope (SEM) map of perovskite.
Fig. 4 is MA1-x-yDMAxCsyPbI3The J-V curve graph of perovskite solar cell device.
Fig. 5 is MA0.905DMA0.07Cs0.025PbI3-zBrzThe J-V curve graph of perovskite solar cell device.
Fig. 6 is MAPbI3、MA0.93DMA0.07PbI3And MA0.905DMA0.07Cs0.025PbI3Three kinds of perovskite solar-electricities
The J-V curve graph in pond.
Specific embodiment
Inventor passes through a large amount of explorative experiments, provides a kind of perovskite material, the perovskite material has
The technical effect of stability under good atmospheric conditions on the solar cell by the application of this perovskite material has higher
Incident photon-to-electron conversion efficiency, complete the present invention on this basis.
The following detailed description of perovskite material according to the present invention, preparation method and its solar cell device.
The perovskite material of first choice explanation according to a first aspect of the present invention.
In perovskite material provided by the present invention, the molecular formula of perovskite is ABX3, wherein A is selected from C1-x-yExFy, institute
State C and be selected from MA and/or FA, the E is selected from DMA, and the F is selected from one or more of Cs, Rb, K, the B be selected from Pb and/
Or Sn, the X are selected from one or more of I, Br and Cl.
In perovskite material provided by the present invention, A is selected from C1-x-yExFy, wherein x=0-0.3, x=0-0.2, x=0-
0.15, x=0-0.03, x=0.03-0.07, x=0.07-0.11, x=0.11-0.1, x=0.1-0.15, x=0.15-
0.2, x=0.2-0.3, preferably x=0-0.2；Y=0-0.3, y=0-0.1, y=0.1-0.2, y=0-0.2, y=0.05-
0.15, y=0-0.01, y=0.01-0.05, y=0.05-0.08, y=0.08-0.15, y=0.15-0.2, y=0.2-
0.3, preferably y=0-0.2.
In perovskite material provided by the present invention, A is selected from MA1-x-yDMAxCsy, wherein x=0-0.15, x=0-0.03,
X=0.03-0.07, x=0.07-0.11, x=0.11-0.1, x=0.1-0.15, preferably x=0.03-0.07；Y=0-0.10,
Y=0.01-0.05, y=0.05-0.08, preferably y=0.01-0.05.
In perovskite material provided by the present invention, A is selected from MA1-x-yDMAxRby, wherein x=0-0.15, x=0-0.03,
X=0.03-0.07, x=0.07-0.11, x=0.11-0.1, x=0.1-0.15, preferably x=0.07-0.11；Y=0-0.10,
Y=0.01-0.05, y=0.05-0.08, preferably y=0.01-0.05.
In perovskite material provided by the present invention, A is selected from MA1-x-yDMAxKy, wherein x=0-0.15, x=0-0.03,
X=0.03-0.07, x=0.07-0.11, x=0.11-0.1, x=0.1-0.15, preferably x=0.07-0.11；Y=0-0.2, y
=0-0.01, y=0.01-0.05, y=0.05-0.15, y=0.15-0.2, preferably y=0.05-0.15.
In perovskite material provided by the present invention, A is selected from FA1-x-yDMAxCsy, wherein x=0-0.2, x=0-0.03,
X=0.03-0.07, x=0.07-0.11, x=0.11-0.1, x=0.1-0.15, x=0.15-0.2, preferably x=0.1-
0.15；Y=0-0.2, y=0-0.01, y=0.01-0.05, y=0.05-0.08, y=0.08-0.15, y=0.15-0.2,
It is preferred that y=0.08-0.15.
In perovskite material provided by the present invention, A is selected from FA1-x-yDMAxRby, wherein x=0-0.2, x=0-0.03,
X=0.03-0.07, x=0.07-0.11, x=0.11-0.1, x=0.1-0.15, x=0.15-0.2, preferably x=0.1-
0.15；Y=0-0.3, y=0-0.01, y=0.01-0.05, y=0.05-0.08, y=0.08-0.15, y=0.15-0.2, y
=0.2-0.3, preferably y=0.1-0.2.
In perovskite material provided by the present invention, A is selected from FA1-x-yDMAxKy, wherein x=0-0.2, x=0-0.03, x
=0.03-0.07, x=0.07-0.11, x=0.11-0.1, x=0.1-0.15, x=0.15-0.2, preferably x=0.1-0.15；
Y=0-0.3, y=0-0.01, y=0.01-0.05, y=0.05-0.08, y=0.08-0.15, y=0.15-0.2, y=
0.2-0.3, preferably y=0.1-0.2.
In perovskite material provided by the present invention, X is selected from I3-zBrz, wherein z=0-3, z=0-1, z=1-2, z=2-
3, preferably z=0-1.
In perovskite material provided by the present invention, perovskite is film and/or polycrystalline.
Secondly the preparation method of the perovskite material of explanation according to a second aspect of the present invention.
The preparation method of perovskite material provided by the present invention, comprising: the precursor solution of perovskite is provided, institute is passed through
It states precursor solution and forms perovskite material.
In perovskite material preparation method for material provided by the present invention, in the precursor solution, precursor solution concentration
Selected from 0.8M-1.4M, 0.8M-1.1M, 1.1M-1.3M, 1.3M-1.4M, preferably 1.1M-1.3M.
In perovskite material preparation method for material provided by the present invention, halide is added in mix reagent, heating stirring obtains
To precursor solution；The halide is selected from dimethyl iodate amine, ditallowdimethyl ammonium bromide, alkyl dimethyl ammonium chloride, methylpyridinium iodide
Amine, methyl bromide ammonium, ammonio methacrylate, carbonamidine hydriodate, carbonamidine hydrobromate, amitraz hydrochloride, cesium iodide, cesium bromide,
Cesium chloride, rubidium iodide, rubidium bromide, rubidium chloride, potassium iodide, potassium bromide, potassium chloride, lead iodide, lead bromide, lead chloride, iodate
Several mixtures of tin, stannic bromide, stannic chloride etc..
In perovskite material preparation method for material provided by the present invention, solvent is selected from organic solvent in the precursor solution,
It is preferably selected from one or more of DMF, DMSO, GBL, NMP, is more preferably selected from DMF and DMSO, the DMSO and DMF's
Volume ratio is 0:1-1:0,0:1-1:9,1:9-1:4,1:4-1:0, is preferably selected from 1:9-1:4.
In perovskite material preparation method for material provided by the present invention, the precursor solution is spin-coated in substrate, the base
Bottom is selected from one of NiOx, PTAA, PEDOT；The substrate with a thickness of 5nm-30nm, 5nm-10nm, 10nm-20nm,
20nm-30nm, preferably 10nm-20nm.
In perovskite material preparation method for material provided by the present invention, the precursor solution uses one-step method spin coating proceeding,
One-step method spin coating proceeding is selected from primary revolving speed 500rpm-2000rpm, 500rpm-1000rp, 1000rpm-1500rpm,
1500rpm-2000rpm, preferably 1000rpm-1500rpm, 10s；Secondary revolving speed 3000rpm-6000rpm, 3000rpm-
4000rpm, 4000rpm-5000rpm, 5000rpm-6000rpm, preferably 4000rpm-5000rpm, 30s.
In perovskite material preparation method for material provided by the present invention, anti-solvent is used in the spin coating process, it is described anti-molten
Agent is selected from one or more of toluene, chlorobenzene, ether.The time that anti-solvent is added dropwise is that spin coating process terminates preceding 8s-20s,
8s-10s, 10s-15s, 15s-20s, preferably 10s-15s are added dropwise, and the amount of anti-solvent is 400uL-800uL, 400uL-
500uL, 500uL-700uL, 700uL-800uL, preferably 500uL-700uL.Perovskite precursor solution is in spin coating process
The solvent such as toluene etc is added dropwise, is nucleated using anti-solvent control perovskite, crystallization and crystal growing process, so that perovskite
Crystalline quality significantly improves, while improving the coverage of film surface.
In perovskite material preparation method for material provided by the present invention, temperature is 70 DEG C -100 DEG C, 70 DEG C -80 when annealing
DEG C, 80 DEG C -95 DEG C, 95 DEG C -100 DEG C, preferably 80 DEG C of -95 DEG C of annealing times are 5Min-15Min, 5Min-8Min, 8 Min-
10Min, 10Min-15Min, preferably 8min-10min.
Furthermore illustrate perovskite material as described above according to a third aspect of the present invention purposes.
The application of perovskite material obtains the device of perovskite material comprising the various perovskite material methods based on the invention
Part, such as perovskite solar battery, optical detector, memory.
Finally, illustrating solar cell device described in the fourth aspect of the present invention.
In solar cell device provided by the present invention, the solar cell device includes transport layer, barrier layer, gold
Belong to the perovskite material of electrode and first aspect present invention.
In solar cell device provided by the present invention, the transport layer includes hole transmission layer and electron-transport
Layer.Its hole-transporting layer is selected from one of NiOx, PTAA, PEDOT or a variety of, electron transfer layer be selected from PCBM and/or
C60。
In solar cell device provided by the present invention, the barrier layer is BCP and/or Zirconium (IV)
acetylacetonate。
In solar cell device provided by the present invention, the metal electrode is metallic silver and/or aluminium.
In solar cell device provided by the present invention, the hole transmission layer with a thickness of 5nm-30nm, 5nm-
10nm, 10nm-20nm, 20nm-30nm, preferably 10nm-20nm, electron transport layer thickness 30nm-100nm, preferably
50nm-80nm, barrier layer thickness 3nm-10nm, 3nm-5nm, 5nm-8nm, 8nm-10nm, preferably 5nm-8nm, metal electricity
Pole is with a thickness of 80nm-150nm, 80nm-100nm, 100nm-120nm, 120nm-150nm, preferably 100nm-120 nm.
In the preparation method of solar cell device provided by the present invention, transport layer is revolved on above-mentioned perovskite material
It applies, then spin coating barrier layer, the sample of preparation is finally subjected to metal electrode, obtained solar cell device is deposited.
The beneficial effects of the present invention are:
1, perovskite material of the invention has the stability under good atmospheric conditions.MAPbI3And MA1-x- yDMAxCsyPbI3Film is put in air, MAPbI after a week3Film will become white, and MA1-x-yDMAxCsyPbI3It is thin
Film is still black, illustrates MA1-x-yDMAxCsyPbI3The stability of film is more preferable.
2, the preparation process of perovskite material of the invention is simple, easy to operate using one-step method film-forming process, has big
The characteristics of large-scale production.
3, perovskite solar cell device incident photon-to-electron conversion efficiency with higher prepared by the present invention.Antistructure at present
Incident photon-to-electron conversion efficiency is usually 16-18%, compared with prior art, the present invention the high 1-2% of incident photon-to-electron conversion efficiency, and the present invention
It can be realized very well using traditional handicraft.Because what is used is all one-step method spin coating proceeding, the synthesis technology phase of ternary and binary
When the material of ternary also compares more at present, and the main advantage of this ternary material of the invention is joined containing there are two methyl
Macromolecular, so that perovskite material is able to maintain a cube phase structure at normal temperature, greatly improve the stabilization of perovskite material
Property.
Illustrate embodiments of the present invention below by way of specific specific example, those skilled in the art can be by this specification
Other advantages and efficacy of the present invention can be easily understood for disclosed content.The present invention can also be by addition different specific
Embodiment is embodied or practiced, and the various details in this specification can also not carried on the back based on different viewpoints and application
From carrying out various modifications or alterations under spirit of the invention.
In the following embodiments, reagent, material and the instrument used such as not special explanation, it is commercially available to obtain
?.
One, the preparation method of perovskite thin film
Embodiment 1
MA0.905DMA0.07Cs0.025PbI3The preparation method of perovskite thin film, specific steps are as follows:
Weigh methylpyridinium iodide amine 0.1871g (MAI, 1.1765mmol), and dimethyl iodate amine 0.0157g (DMAI, 0.091
Mmol), cesium iodide 0.0084g (CsI, 0.0325mmol) and lead iodide 0.5993g (1.3mmol) are added to equipped with 1ml DMF
In the mix reagent of DMSO in the 4ml vial of (volume ratio 4:1), 70 DEG C at a temperature of stir 1 hour, it is cooling, use
The polytetrafluoroethylene (PTFE) filter of 0.22um filters, and acquired solution is perovskite precursor solution.Nickel oxide-base bottom is placed in spin coating
It on instrument, with 200ul liquid-transfering gun perovskite precursor solution drop on nickel oxide-base bottom, closes the lid, starts spin coating, spin coating ginseng
Number is 1000rpm, 10s；4000rpm, 30s measure 600ul toluene with 1ml liquid-transfering gun in 15s before spin coating process terminates and make
For anti-solvent, quickly drop is in the substrate of rotation, and after spin coating process, taking-up substrate, which is placed on warm table, to be heated, heating temperature
Degree is 90 DEG C, heating time 8min, and heating terminates to obtain black perovskite thin film.Fig. 1 is MA1-x-yDMAxCsyPbI3Perovskite
The X ray diffracting spectrum of film.
Embodiment 2
MA0.88DMA0.07Cs0.05PbI3The preparation method of perovskite thin film, specific steps are as follows:
Weigh methylpyridinium iodide amine 0.1819g (MAI, 1.144mmol), and dimethyl iodate amine 0.0157g (DMAI, 0.091
Mmol), cesium iodide 0.0169g (CsI, 0.065mmol) and lead iodide 0.5993g (1.3mmol) are added to equipped with 1ml DMF
In the mix reagent of DMSO in the 4ml vial of (volume ratio 4:1), 70 DEG C at a temperature of stir 1 hour, it is cooling, use
The polytetrafluoroethylene (PTFE) filter of 0.22um filters, and acquired solution is perovskite precursor solution.Nickel oxide-base bottom is placed in spin coating
It on instrument, with 200ul liquid-transfering gun perovskite precursor solution drop on nickel oxide-base bottom, closes the lid, starts spin coating, spin coating ginseng
Number is 1000rpm, 10s；4000rpm, 30s measure 600ul toluene with 1ml liquid-transfering gun in 15s before spin coating process terminates and make
For anti-solvent, quickly drop is in the substrate of rotation, and after spin coating process, taking-up substrate, which is placed on warm table, to be heated, heating temperature
Degree is 90 DEG C, heating time 8min, and heating terminates to obtain black perovskite thin film.Fig. 1 is MA1-x-yDMAxCsyPbI3Perovskite
The X ray diffracting spectrum of film.
Embodiment 3
MA0.855DMA0.07Cs0.075PbI3The preparation method of perovskite thin film, specific steps are as follows:
Weigh methylpyridinium iodide amine 0.1767g (MAI, 1.1115mmol), and dimethyl iodate amine 0.0157g (DMAI, 0.091
Mmol), cesium iodide 0.02533g (CsI, 0.0975mmol) and lead iodide 0.5993g (1.3mmol) are added to equipped with 1ml DMF
In the mix reagent of DMSO in the 4ml vial of (volume ratio 4:1), 70 DEG C at a temperature of stir 1 hour, it is cooling, use
The polytetrafluoroethylene (PTFE) filter of 0.22um filters, and acquired solution is perovskite precursor solution.Nickel oxide-base bottom is placed in spin coating
It on instrument, with 200ul liquid-transfering gun perovskite precursor solution drop on nickel oxide-base bottom, closes the lid, starts spin coating, spin coating ginseng
Number is 1000rpm, 10s；4000rpm, 30s measure 600ul toluene with 1ml liquid-transfering gun in 15s before spin coating process terminates and make
For anti-solvent, quickly drop is in the substrate of rotation, and after spin coating process, taking-up substrate, which is placed on warm table, to be heated, heating temperature
Degree is 90 DEG C, heating time 8min, and heating terminates to obtain black perovskite thin film.Fig. 1 is MA1-x-yDMAxCsyPbI3Perovskite
The X ray diffracting spectrum of film.
Embodiment 4
MA0.83DMA0.07Cs0.1PbI3The preparation method of perovskite thin film, specific steps are as follows:
Weigh dimethyl iodate amine 0.0157g (DMAI, 0.091mmol), and methylpyridinium iodide amine 0.1715g (MAI, 1.079
Mmol), cesium iodide 0.0337g (CsI, 0.13mmol) and lead iodide 0.5993g (1.3mmol) be added to equipped with 1ml DMF and
In the mix reagent of DMSO in the 4ml vial of (volume ratio 4:1), 70 DEG C at a temperature of stir 1 hour, it is cooling, use
The polytetrafluoroethylene (PTFE) filter of 0.22um filters, and acquired solution is perovskite precursor solution.Nickel oxide-base bottom is placed in spin coating
It on instrument, with 200ul liquid-transfering gun perovskite precursor solution drop on nickel oxide-base bottom, closes the lid, starts spin coating, spin coating ginseng
Number is 1000rpm, 10s；4000rpm, 30s measure 600ul toluene with 1ml liquid-transfering gun in 15s before spin coating process terminates and make
For anti-solvent, quickly drop is in the substrate of rotation, and after spin coating process, taking-up substrate, which is placed on warm table, to be heated, heating temperature
Degree is 90 DEG C, heating time 8min, and heating terminates to obtain black perovskite thin film.Fig. 1 is MA1-x-yDMAxCsyPbI3Perovskite
The X ray diffracting spectrum of film.
Embodiment 5
MA0.905DMA0.07Cs0.025PbI2.8Br0.2The preparation method of perovskite thin film, specific steps are as follows:
Weigh methylpyridinium iodide amine 0.1871g (MAI, 1.1765mmol), and dimethyl iodate amine 0.0157g (DMAI, 0.091
Mmol), cesium iodide 0.0084g (CsI, 0.0325mmol), lead iodide 0.5394g (1.17mmol) and lead bromide 0.0477g
(0.13mmol) is added in the 4ml vial of (volume ratio 4:1) in the mix reagent equipped with 1ml DMF and DMSO, 70
It is stirred 1 hour at a temperature of DEG C, it is cooling, it is filtered with the polytetrafluoroethylene (PTFE) filter of 0.22um, acquired solution is perovskite precursor
Solution.Nickel oxide-base bottom is placed on spin coating instrument, is dripped with 200ul liquid-transfering gun perovskite precursor solution at nickel oxide-base bottom
On, it closes the lid, starts spin coating, spin coating parameters are 1000rpm, 10s；4000rpm, 30s, the 15s before spin coating process terminates
When use 1ml liquid-transfering gun to measure 600ul toluene as anti-solvent, quickly drip in the substrate of rotation, after spin coating process, take
Substrate is placed on warm table and heats out, and heating temperature is 90 DEG C, heating time 8min, and it is thin that heating end obtains black perovskite
Film.Fig. 2 is MA0.905DMA0.07Cs0.025PbI3-zBrzThe X ray diffracting spectrum of perovskite thin film.
Embodiment 6
MA0.905DMA0.07Cs0.025PbI2.6Br0.4The preparation method of perovskite thin film, specific steps are as follows:
Weigh methylpyridinium iodide amine 0.1871g (MAI, 1.1765mmol), and dimethyl iodate amine 0.0157g (DMAI, 0.091
Mmol), cesium iodide 0.0084g (CsI, 0.0325mmol), lead iodide 0.4794g (1.04mmol) and lead bromide 0.0954g
(0.26mmol) is added in the 4ml vial of (volume ratio 4:1) in the mix reagent equipped with 1ml DMF and DMSO, 70
It is stirred 1 hour at a temperature of DEG C, it is cooling, it is filtered with the polytetrafluoroethylene (PTFE) filter of 0.22um, acquired solution is perovskite precursor
Solution.Nickel oxide-base bottom is placed on spin coating instrument, is dripped with 200ul liquid-transfering gun perovskite precursor solution at nickel oxide-base bottom
On, it closes the lid, starts spin coating, spin coating parameters are 1000rpm, 10s；4000rpm, 30s, the 15s before spin coating process terminates
When use 1ml liquid-transfering gun to measure 600ul toluene as anti-solvent, quickly drip in the substrate of rotation, after spin coating process, take
Substrate is placed on warm table and heats out, and heating temperature is 90 DEG C, heating time 8min, and it is thin that heating end obtains black perovskite
Film.Fig. 2 is MA0.905DMA0.07Cs0.025PbI3-zBrzThe X ray diffracting spectrum of perovskite thin film.
Embodiment 7
MA0.905DMA0.07Cs0.025PbI2.4Br0.6The preparation method of perovskite thin film, specific steps are as follows:
Weigh methylpyridinium iodide amine 0.1871g (MAI, 1.1765mmol), and dimethyl iodate amine 0.0157g (DMAI, 0.091
Mmol), cesium iodide 0.0084g (CsI, 0.0325mmol), lead iodide 0.4195g (0.91mmol) and lead bromide 0.1431g
(0.39mmol) is added in the 4ml vial of (volume ratio 4:1) in the mix reagent equipped with 1ml DMF and DMSO, 70
It is stirred 1 hour at a temperature of DEG C, it is cooling, it is filtered with the polytetrafluoroethylene (PTFE) filter of 0.22um, acquired solution is perovskite precursor
Solution.Nickel oxide-base bottom is placed on spin coating instrument, is dripped with 200ul liquid-transfering gun perovskite precursor solution at nickel oxide-base bottom
On, it closes the lid, starts spin coating, spin coating parameters are 1000rpm, 10s；4000rpm, 30s, the 15s before spin coating process terminates
When use 1ml liquid-transfering gun to measure 600ul toluene as anti-solvent, quickly drip in the substrate of rotation, after spin coating process, take
Substrate is placed on warm table and heats out, and heating temperature is 90 DEG C, heating time 8min, and it is thin that heating end obtains black perovskite
Film.Fig. 2 is MA0.905DMA0.07Cs0.025PbI3-zBrzThe X ray diffracting spectrum of perovskite thin film.
Embodiment 8
FA0.8DMA0.1Cs0.1PbI3The preparation method of perovskite thin film, specific steps are as follows:
Weigh iodine carbonamidine 0.1789g (FAI, 1.04mmol), dimethyl iodate amine 0.0225g (DMAI, 0.13mmol), iodine
Change caesium 0.0338g (CsI, 0.13mmol), lead iodide 0.5993g (1.3mmol) is added to mixed equipped with 1ml DMF and DMSO
Close in reagent in the 4ml vial of (volume ratio 4:1), 70 DEG C at a temperature of stir 1 hour, it is cooling, it is poly- with 0.22um
The filtering of tetrafluoroethene filter, acquired solution are perovskite precursor solution.Nickel oxide-base bottom is placed on spin coating instrument, is used
200ul liquid-transfering gun perovskite precursor solution is dripped on nickel oxide-base bottom, is closed the lid, and spin coating is started, and spin coating parameters are,
1000rpm,10s；4000rpm, 30s, used in 10s before spin coating process terminates 1ml liquid-transfering gun measure 200ul toluene as instead it is molten
Agent, quickly drop is in the substrate of rotation, and after spin coating process, taking-up substrate, which is placed on warm table, to be heated, and heating temperature is
120 DEG C, heating time 10min, heating terminates to obtain black perovskite thin film.
Two, the preparation method of perovskite solar cell device
Embodiment 9
MA1-x-yDMAxCsyPbI3The preparation of perovskite battery
Ready-made perovskite thin film is placed on spin coating instrument, the PCBM- chlorine of 80ul 20mg/ml is measured with 200ul liquid-transfering gun
Benzole soln drips on perovskite thin film, spin coating, parameter 1000rpm, 32s.After spin coating process, measured with 1ml liquid-transfering gun
60ul BCP saturation isopropanol is dissolved in, and is added dropwise while rotating, is dripped off BCP in spin coating parameters 6000rpm, 40s, 2-3s
Solution.After to spin coating process, the sample of sample surrounding (4mm width) is wiped off with blade, and dip in acetonitrile reagent with cotton swab and wipe
Completely, then sample is sent into plated film instrument and carries out metal electrode vapor deposition, vacuum values 5*10-7Torr, metallic silver with a thickness of
120nm.Fig. 4 is MA1-x-yDMAxCsyPbI3The J-V curve graph of perovskite solar cell device.
Embodiment 10
MA0.905DMA0.07Cs0.025PbI3-zBrzThe preparation of perovskite battery
Ready-made perovskite thin film is placed on spin coating instrument, the PCBM- chlorine of 80ul 20mg/ml is measured with 200ul liquid-transfering gun
Benzole soln drips on perovskite thin film, spin coating, parameter 1000rpm, 32s.After spin coating process, measured with 1ml liquid-transfering gun
60ul BCP saturation isopropanol is dissolved in, and is added dropwise while rotating, is dripped off BCP in spin coating parameters 6000rpm, 40s, 2-3s
Solution.After to spin coating process, the sample of sample surrounding (4mm width) is wiped off with blade, and dip in acetonitrile reagent with cotton swab and wipe
Completely, then sample is sent into plated film instrument and carries out metal electrode vapor deposition, vacuum values 5*10-7Torr, metallic silver with a thickness of
120nm.Fig. 5 is MA0.905DMA0.07Cs0.025PbI3-zBrzThe J-V curve graph of perovskite solar cell device.
Embodiment 11
FA0.8DMA0.1Cs0.1PbI3The preparation of perovskite battery
Ready-made perovskite thin film is placed on spin coating instrument, the PCBM- chlorine of 80ul 20mg/ml is measured with 200ul liquid-transfering gun
Benzole soln drips on perovskite thin film, spin coating, parameter 1000rpm, 32s.After spin coating process, measured with 1ml liquid-transfering gun
60ul BCP saturation isopropanol is dissolved in, and is added dropwise while rotating, is dripped off BCP in spin coating parameters 6000rpm, 40s, 2-3s
Solution.After to spin coating process, the sample of sample surrounding (4mm width) is wiped off with blade, and dip in acetonitrile reagent with cotton swab and wipe
Completely, then sample is sent into plated film instrument and carries out metal electrode vapor deposition, vacuum values 5*10-7Torr, metallic silver with a thickness of
120nm。
Comparative example 12
Respectively to based on MAPbI3,MA0.93DMA0.07PbI3And MA0.905DMA0.07Cs0.025PbI3Three kinds of perovskite sun
Energy battery compares, and the J-V curve of perovskite solar battery is as shown in fig. 6, MA0.905DMA0.07Cs0.025PbI3Ternary
The photoelectric conversion efficiency of perovskite is higher than MAPbI3,MA0.93DMA0.07PbI3The efficiency of perovskite solar battery.
Three, the efficiency test of perovskite solar cell device
Test equipment are as follows: solar simulator, K2400
Test parameter are as follows: light intensity: 100mw/cm2
Scanning range: -0.1-1.13V
Scanning speed: 10mV/s
Residence time: 200ms
Fig. 4 and Fig. 5 is the J-V curve graph of perovskite solar cell device.
By Fig. 1 and Fig. 2 it is found that MA1-x-yDMAxCsyPbI3And MA0.905DMA0.07Cs0.025PbI3-zBrzPerovskite thin film is all
Show the feature of cubic phase.From the figure 3, it may be seen that prepared MA1-x-yDMAxCsyPbI3Perovskite solar cell device it is each
Thickness degree and MA0.905DMA0.07Cs0.025PbI3And MA0.88DMA0.07Cs0.05PbI2.6Br0.4(a:ITO/NiOx/ in Fig. 3
MA1-x-yDMAxCsyPbI3/PCBM/BCP/Ag,b:MA0.905DMA0.07Cs0.025PbI3,c:
MA0.88DMA0.07Cs0.05PbI2.6Br0.4) perovskite thin film surface topography.As shown in Figure 4, MA1-x-yDMAxCsyPbI3Calcium titanium
Mine solar cell device all shows good photoelectric conversion efficiency, wherein being based on MA0.905DMA0.07Cs0.025PbI3Device
Part has highest incident photon-to-electron conversion efficiency, is 19.37%.As shown in Figure 5, in MA0.905DMA0.07Cs0.025PbI3Perovskite knot
Bromide ion (Br) is added in structure can reduce the efficiency of perovskite, but open-circuit voltage improves.It will be appreciated from fig. 6 that this hair
The efficiency of bright ternary perovskite solar battery is higher than the efficiency of other units or binary perovskite solar battery.
Claims (10)
1. a kind of perovskite material, the molecular formula of the perovskite is ABX3, wherein the A is selected from C1-x-yExFy, the C is selected from
MA and/or FA, the E are selected from DMA, and the F is selected from one or more of Cs, Rb, K, and the B is selected from Pb and/or Sn, described
X is selected from one or more of I, Br and Cl.
2. perovskite material according to claim 1, which is characterized in that the C1-x-yExFyMiddle x=0-0.3, y=0-
0.3, preferably x=0-0.2, y=0-0.2.
3. perovskite material according to claim 1, which is characterized in that the A is selected from MA1-x-yDMAxCsy, X is selected from I3- zBrz, wherein z=0-3.
4. perovskite material according to claim 1, which is characterized in that the perovskite material is film and/or polycrystalline.
5. the preparation method of perovskite material described in -4 any claims according to claim 1, comprising: provide perovskite
Precursor solution forms perovskite material by the precursor solution.
6. the preparation method of perovskite material according to claim 5, which is characterized in that the precursor solution concentration is
0.8M-1.4M, solvent is selected from organic solvent in the precursor solution, be preferably selected from one of DMF, DMSO, GBL, NMP or
It is several.
7. the preparation method of perovskite material according to claim 5, which is characterized in that the precursor solution is spin-coated on
In substrate, the substrate is selected from one of NiOx, PTAA, PEDOT；Anti-solvent is used in the spin coating process, it is described anti-molten
Agent is selected from one or more of toluene, chlorobenzene, ether.
8. the preparation method of perovskite material according to claim 5, which is characterized in that further include the step of annealing
Suddenly, temperature is 70 DEG C -100 DEG C when the annealing, annealing time 5Min-10Min.
9. perovskite material described in -4 any claims is in solar battery or electroluminescent device according to claim 1
Purposes.
10. a kind of solar cell device, including transport layer, barrier layer, metal electrode and perovskite material, the perovskite
Material is perovskite material described in claim 1-4 any claim.
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